5.

3 Hard and Soft Acids and Bases

The ease with which an acid-base reaction occurs depends on the strength of both
the acid and the base. Strong acids and bases are generally more reactive than
weak acids and bases. However, the direction of the reaction and the stability of the
products often depend on another quality—the hardness or softness of the acid
and base. Although chemists have not created a quantitative measure to describe
the qualities that makes an acid or base hard or soft, they do describe them
qualitatively. As you look at the following list of characteristics that describe hard
and soft acids and bases, remember that an acid has an empty orbital and an
unfilled valence shell, and a base has in its valence shell a pair of nonbonding
electrons that is available for donation.

Soft Acids. For soft acids, the electron-pair acceptor atoms are large, have a low
positive charge density, and contain unshared pairs of electrons in their valence
shells. The unshared pairs of electrons are in the p or d orbitals. Also, soft acids have
a high polarizability and a low electronegativity. In organic chemistry, the soft
acids usually include only the halogens, phosphorus, and sulfur compounds.

Hard Acids. For hard acids, the acceptor atoms are small, have a high positive charge
density, and contain no unshared pairs of electrons in their valence shells. They
have a low polarizability and a high electronegativity. The hydrogen ion is a good
example of a hard acid.

Hardness or softness is a qualitative measure of the reactivity of acids and bases. Hard or soft is
independent of strength or weakness of acids and bases.

Charge density is the volume of space occupied by a charge. A large ion has a lower charge density
than a small ion does.

Polarizability means the ability of an atom to have a distorted distribution of electrons.

Soft Bases. For soft bases, the donor atoms hold their valence electrons loosely.
They have high polarizability, low negative charge density, and low
electronegativity. Common soft bases are the cyanide (-CN) and iodide (I -)
ions.
Hard Bases. For hard bases, the donor atoms are small, have a high negative
charge density, and hold their valence electrons tightly. They have a low
polarizability and a high electronegativity. The hydroxide ion is a good
example of a hard base.
To visualize a polarizable atom, imagine that an atom is a large floppy ball and you
are holding it cupped in both hands. The ball tends to be spherical, but, as you shift
one hand higher than the other, it easily deforms. If you raise your left hand a little,
the portion of the ball in your right hand becomes larger. Then, if you raise your
right hand a little, the portion of the ball in your left hand becomes larger. A
polarizable atom shifts its electron density from one part of the atom to another: at
one instant, one portion of the atom has the higher electron density; then the next
instant, another portion has the higher electron density.

Bond Polarity Versus Polarizability

Bond polarity differs from polarizability. In a polar bond, the more electronegative atom of the bonded
pair pulls the bonding electrons toward itself. A polarizable atom or group can momentarily shift
electron density from one portion of the atom or group to another.

For the concepts of hardness or softness of acids and bases to be of value to you, you must
be able to differentiate between them. To do this, your most useful tool is the periodic table.
A general rule is that hardness goes to softness moving from the top to the bottom on the
periodic table because the size of the atoms increases with increasing numbers of electrons.
A larger acid or base has a lower charge density and is more polarizable. For example, base
softness in Group VII A on the periodic table decreases in this order: I - > Br- > Cl- > F-. Also,
the elements on the left side tend to be acids, and elements on the right side tend to be
bases. In this way, chemists approximately rank acids and bases in order of hardness or
softness. Base softness within a period on the periodic table decreases in order of increasing
electronegativity; for example, -CH3 > -NH2 > -OH > F-.
Hardness and softness are difficult to quantify. Rather than relying specifically on
these types of sequences, chemists divide acids and bases into three groups: (1)
hard acids or bases, (2) soft acids or bases, and (3) borderline acids or bases. Table 5.2 lists a
few examples of each category.
Table 5.2. Some examples of hard and soft acids and bases. (R represents an alkyl group.)

H+ is a hard acid because it has no electrons and has a high positive charge density. The H - ion is a soft
base because it has a pair of electrons and only one proton, so it holds the electrons rather loosely.
Thus, it is quite polarizable and soft.

An important rule concerning acid-base reactions is that hard acids prefer to bond with hard bases, and
soft acids prefer to bond with soft bases. This rule, often called the HSAB Principle, has nothing to
do with acid or base strength, but merely states that a bond between a particular acid and a particular
base has extra stability if both are either hard or soft. The HSAB Principle also helps to predict the
outcome of an acid-base reaction. For example, the acyl group (RCO ⊕) is a hard Lewis acid and forms
stable combinations with hard Lewis bases such as -NH2, RO-, and Cl-. In contrast, it forms marginally
stable or even unstable compounds with soft Lewis bases such as RS- and I-.

The HSAB principle is the preference for hard bases to form bonds with hard acids and soft bases to
form bonds with soft acids.

Perhaps the most important application of the HSAB Principle is in determining whether a particular
compound will act as a base or as a nucleophile. Generally, a soft base is a good nucleophile, and a hard
base is a better base. Chapters 12 through 14 show this rule of thumb in action. The statement was
made earlier that a nucleophile generally reacts with a positive or partially positive carbon, and a base
generally reacts with a positive or partially positive hydrogen. This statement is a simplified form of the
HSAB principle: H+ is a much harder acid than C+, so it tends to react with a harder base than C + does.
For example, chlorocyclohexane reacts with a hydroxide ion to remove a proton from the carbon
adjacent to the carbon bearing the chlorine. This reaction forms a double bond.
The difference between these two reactions is that the hydroxide ion is a hard base, whereas the
cyanide ion is a soft base. The hydroxide ion removes a proton; the cyanide ion reacts with the carbon
bearing the chlorine to displace the chlorine.

Thus far, this chapter has presented acids and bases in a broad sense. It covered the different theories of
acidity and basicity and how to estimate their relative strengths. It also showed how acids and bases
react with each other. Section 5.4 applies these concepts specifically to organic acids and bases.